Role of organic cations in tuning the exciton binding energy of 2D lead iodide perovskite derivatives

Control over the exciton binding energy (Eb) in two-dimensional (2D) perovskites can enable their application in a broad range of optoelectronic technologies. To investigate the effects of organic cations on the excitonic properties of 2D perovskites, films of lead iodide hybrids basing on four structurally similar cations of phenylethylammonium (PEA), 4-florophenylethylammonium (FPEA), 4-chlorophenylethylammonium (ClPEA) and 4-bromophenylethylammonium (BrPEA) were prepared and their optical properties were characterized. Results show that both the perovskite layer distortion and exciton absorption/emission peak do not vary too much by the substitution of halogen atom in the para H of phenylethyl cation. Further examination of the temperature-dependent exciton emission properties reveals that the thermal activation energy Ea, which can also be regarded as exciton binding energy in our work, can be tuned over ca. 170 meV within the set of hybrids. It is found that exciton binding energy is sensitive to the identity of organic cations and to the resulting PbI6 octahedron distortion. Among the compounds considered, FPEA based perovskite has the biggest PbI6 octahedron distortion and the largest calculated Ea of 330 meV, while the Br-PEA based perovskite shows a smaller octahedron distortion and the lowest calculated Ea. We believe that an enhanced polarizability of organic cations may be responsible for the observed decrease in octahedra distortion and Ea for the p-halophenylethylammonium lead iodide perovskite derivatives.